EP0743281A1 - Procédé pour l'enrichissement en oxygène de l'air par adsorption d'air avec des mélanges de zéolithes à tamis moléculaires - Google Patents

Procédé pour l'enrichissement en oxygène de l'air par adsorption d'air avec des mélanges de zéolithes à tamis moléculaires Download PDF

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Publication number
EP0743281A1
EP0743281A1 EP96107132A EP96107132A EP0743281A1 EP 0743281 A1 EP0743281 A1 EP 0743281A1 EP 96107132 A EP96107132 A EP 96107132A EP 96107132 A EP96107132 A EP 96107132A EP 0743281 A1 EP0743281 A1 EP 0743281A1
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Prior art keywords
zeolite
cao
air
ratio
adsorber
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EP96107132A
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German (de)
English (en)
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EP0743281B1 (fr
Inventor
Gerhard Reiss
Lothar Dr. Puppe
Bruno Hees
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0259—Physical processing only by adsorption on solids
    • C01B13/0262—Physical processing only by adsorption on solids characterised by the adsorbent
    • C01B13/027—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/12—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/403—Further details for adsorption processes and devices using three beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B01D53/0476—Vacuum pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0046—Nitrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S95/00—Gas separation: processes
    • Y10S95/90—Solid sorbent
    • Y10S95/902—Molecular sieve

Definitions

  • the present invention relates to an improved method for oxygen enrichment of air using vacuum swing adsorption (VSA) and / or pressure swing adsorption (PSA).
  • VSA vacuum swing adsorption
  • PSA pressure swing adsorption
  • VSA vacuum swing adsorption
  • PSA pressure swing adsorption
  • a continuous process is achieved in the VSA process by the following process steps: a) passing air through a bed of zeolite at atmospheric pressure; O 2 -rich gas is withdrawn at the outlet side; b) evacuating the bed with a vacuum pump to a negative pressure of about 100 to 300 mbar in counterflow of the air flow; c) Filling the bed with O 2 -rich gas to 1 atm in counterflow to the air flow (see for example Fig. 1).
  • step b) is carried out at about 1 atm with purging with part of the O 2 -rich gas.
  • the separation is carried out at transatmospheric pressure, for example at 1.1 to 2 bar and the desorption at about 200 to 500 mbar (minimum pressure).
  • the cost-effectiveness of such systems is determined by the investment, such as the amount of adsorbent, the size of the vacuum pump, and in particular by the operating costs, such as power consumption of the vacuum pumps.
  • Zeolites were therefore produced with which it is possible to achieve high nitrogen adsorption, so that the amount of zeolite used could be reduced.
  • Such Ca zeolites A are described in EP-A-128 545.
  • An oxygen enrichment process is known from JP 87/148 304, in which an adsorber with special arrangements of different types of zeolite is used instead of an adsorber with a zeolite bed.
  • the adsorber contains zeolites of the Na-X, Na-Y or Ca-X type on the air inlet side and of the Ca-Na-A type on the air outlet side.
  • Example 3 of EP-A-374 631 a CaA zeolite with low N 2 adsorption is used in the air entry zone and a CaA zeolite with high N 2 adsorption is used in the exit zone, the CaO / Al 2 O 3 content the zeolite of Example 3 is approximately the same size (0.75 CaO / Al 2 O 3 ).
  • the different N 2 loads result from different activations.
  • the object of the present invention was to provide an energy-efficient VSA-PVSA method for oxygen enrichment of air with the aid of an improved O 2 yield, ie an improved N 2 -O 2 selectivity of the total fill.
  • the oxygen enrichment of air by means of certain combinations of special zeolite beds with increased O 2 yield or reduced energy consumption can be carried out at air temperatures of 20 to 50 ° C., with a Ca zeolite X in the air inlet zone of the adsorber is located, whose CaO / Al 2 O 3 ratio is 0.4 to 0.75.
  • the invention relates to a method for oxygen enrichment of air at temperatures from 20 to 50 ° C by means of vacuum swing adsorption (VSA) or pressure swing adsorption (PSA) or by means of a combination of VSA and PSA, in which the air passes through an adsorber is passed, which is filled with beds of zeolite granules, which is characterized in that there are at least two beds in the adsorber, the bed on the air inlet side of the adsorber made of Na-Ca zeolite X with an SiO 2 / Al 2 O 3 Ratio of 2.0 to 2.5 and with a CaO / Al 2 O 3 ratio of 0.4 to 0.75, which is adapted to the air inlet temperature, and the bed on the air outlet side of the adsorber from Na-Ca Zeolite A with a CaO / Al 2 O 3 ratio of 0.5 to 1.0 or consists of Na-Ca zeolite X with a CaO / Al 2 O 3 ratio which is above the CaO
  • the CaO / Al 2 O 3 ratio of the Na-Ca zeolite X at the inlet zone is 0.4 to 0.6, at an air inlet temperature of 30 to 40 ° C 0.55 to 0.65 and at an air inlet temperature of 40 to 50 ° C 0.6 to 0.75.
  • the bed is preferably present on the air inlet side of the adsorber in an amount of 25 to 75% by weight, particularly preferably 25 to 50% by weight, based on the total amount of the beds.
  • the proportion of the bed on the air outlet side in particular when it is Na-Ca zeolite X with a CaO / Al 2 O 3 ratio of 0.75 to 1.0, the higher the temperature of the air, the higher is the air inlet side of the adsorber.
  • the Na-Ca zeolites X used preferably have an SiO 2 / Al 2 O 3 ratio of 2.0 to 3.0, particularly preferably 2.0 to 2.5.
  • the zeolite beds are preferably one zeolite per bed.
  • the zeolite can also be present in a bed with different Ca contents, the zeolite preferably having the higher Ca contents in the direction of the air outlet.
  • the method according to the invention is carried out in principle like conventional PSA or VSA methods. Such methods are e.g. in Gas Separation and Purification 1991, Vol 5, June, pages 89 to 90.
  • zeolites exchanged with other cations can also be used.
  • the calcium can be partially or completely replaced by strontium or magnesium (see also US Pat. No. 3,313,091).
  • a layer of gas consisting of e.g. made of silica gel, before the actual adsorption layers.
  • Na-Ca zeolite X granules were produced in accordance with EP-A 0 170 026, Example 15, the treatment with CaCl 2 solution being carried out 3 times and calcination at 600 ° C. using dry nitrogen.
  • the Ca content was a CaO / Al 2 O 3 ratio of 0.96.
  • the SiO 2 / Al 2 O 3 ratio of the zeolite was 2.35.
  • Na-Ca zeolite X granules were produced in accordance with EP-A 0 170 026, Example 15, the treatment with CaCl 2 solution being carried out once with reduced exchange time and calcination at 600 ° C. using dry nitrogen.
  • the Ca content was at a CaO / Al 2 O 3 ratio of 0.6.
  • the SiO 2 / Al 2 O 3 ratio of the zeolite was 2.35.
  • a Na-Ca zeolite A granulate was produced in accordance with EP-A 0 170 026, example 2.
  • the calcination was carried out with nitrogen at 500 to 600 ° C.
  • the Ca content was at a CaO / Al 2 O 3 ratio of 0.72.
  • Na-Ca zeolite X granules were produced in accordance with EP-A 0 170 026, Example 15, the treatment with CaCl 2 solution being carried out once with reduced exchange time and calcining at 600 ° C. using dry nitrogen.
  • the Ca content was at a CaO / Al 2 O 3 ratio of 0.43.
  • the SiO 2 / Al 2 O 3 ratio of the leolith was 2.35.
  • Na-Ca zeolite X granules were prepared in accordance with EP-A 0 170 026, Example 15, the treatment with CaCl 2 solution being carried out once and calcining at 600 ° C. using dry nitrogen.
  • the Ca content was at a CaO / Al 2 O 3 ratio of 0.72.
  • the SiO 2 / Al 2 O 3 ratio of the zeolite was 2.35.
  • a Na-Ca zeolite A granulate was produced in accordance with EP-A 0 170 026, example 2, and activated with dry air at 600 ° C.
  • the Ca content was at a CaO / Al 2 O 3 ratio of 0.72.
  • Na-Ca zeolite X granules were prepared in accordance with EP-A 0 170 026, Example 15, the treatment with CaCl 2 solution being carried out twice and calcining at 600 ° C. using dry nitrogen.
  • the Ca content was at a CaO / Al203 ratio of 0.83.
  • the SiO2 / Al203 ratio of the zeolite was 2.35.
  • FIG. 1 The plant in which the oxygen enrichment was carried out is shown schematically in FIG. 1.
  • Ambient air is introduced via blower G, heater H, valve 11A into adsorber A (at 1 bar (abs), with 75% relative humidity).
  • Oxygen-rich gas is drawn off as a product via valve 14A, blower R (at 1 bar (abs)).
  • Air separation time is 1 minute; Valves 12A, 13A are closed. Various temperatures of the incoming air can be set via the heater H.
  • adsorber B is evacuated to 200 mbar via valve 12B and vacuum pump V, valves 11B, 13B, 14B of adsorber B being closed.
  • adsorber C is filled with oxygen-rich gas (product) via valve 15, valve 13C, from 200 mbar to 1 bar (abs) within one minute, valves 11C, 12C, 14C being closed.
  • the suction power of the vacuum pump V and thus the final pressure of the vacuum can be changed.
  • the amount of gas produced was measured with an O 2 volume concentration of 90% and the amount of air supplied via the fan G.
  • Sample A was used in the adsorber.
  • the residual H 2 -O loading of the activated zeolite was below 0.5% by weight (according to DIN 8948; P 2 O 5 method).
  • the amount of zeolite per adsorber was 905 kg.
  • the oxygen enrichment was carried out according to the above statements. The following data were determined: Air temperature at inlet [° C] 30th 40 Product quantity [Nm 3 / h] 44 46.5 O 2 yield [%] 37 43
  • Sample B was used in the adsorber (905 kg / adsorber).
  • the residual H 2 O loading of the activated zeolite was below 0.5% by weight.
  • the following data were determined: Air temperature at inlet [° C] 30th 40
  • Example 9 (comparison, according to EP-A 0 374 631, Example 3)
  • sample A with the high Ca content of 0.96 should have better properties in the O 2 enrichment than sample B with the average Ca content of 0.6. Contrary to previous knowledge, however, sample B (example 2) has a higher yield than sample A (example 1) in the examined temperature range from 30 to 40 ° C.
  • the Ca zeolite A (sample C) used has better properties than sample B. It was therefore surprising that the yields from the combination of samples B and C were even better than those from the bed of Sample C were reached.
  • Example 10 shows in comparison to Example 3 that although an arrangement of two Ca zeolite A beds improves the yield, this improvement is only about 1% (abs.) And thus far below the advantageous establishment of a zone a Ca zeolite X lies at the inlet of the adsorber.
  • the Ca content of the Ca zeolite X apparently influences the N2 / O2 selectivity.
  • the N2 loading of the individual component isotherms is increased with the Ca content, but is hardly noticeable in the dynamic air separation process.
  • Example 4 shows that the Ca zeolite X used with a very high CaO content (sample A; 0.96 CaO) in the region of the entry zone at usual entry temperatures of 20 to 50 ° C. has no improved yields compared to the pure Ca zeolite A ( Example 3) provides.
  • Table 2 shows that, for example in the range from 30 to 40 ° C., the CaO / Al 2 O 3 ratio should be approximately 0.6 in the Ca zeolite X in the entry zone.
  • the yields of this arrangement (Example 6) are significantly higher than the expected arithmetic mean of the arrangements from Example 7 (0.43 CaO / Al 2 O 3 ) and Example 8 (0.72 CaO / Al 2 O 3 ).
  • Example 7 according to the invention with Ca zeolite X in the entry zone with a CaO / Al 2 O 3 ratio of 0.43 shows better yields than Example 6 with Ca zeolite X with 0.6 CaO / Al 2 O 3 and also better properties than Example 3 (bed consisting only of CaA zeolite).
  • Example 4 shows that in the entry zone the Ca zeolite X with a high Ca exchange rate of 0.96 cannot be used for temperatures from 20 to 50 ° C. and at 20 to 50 ° C. worse than a Ca zeolite X with a lower CaO Content is.
  • example 8 according to the invention with Ca zeolite X with 0.72 CaO / Al 2 O 3 shows better yields in the entry zone than the combination with Ca zeolite X with 0.96 CaO / Al 2 O 3 and also better properties than the bed in Example 3 (consisting only of CaA zeolite).
  • Example 5 shows that in the temperature range of the incoming air from 30 to 40 ° C., a bed of exchanged Ca zeolite X (sample B) in the entry zone and highly exchanged Ca zeolite X in the exit zone (sample A) better O 2 yields delivers as the corresponding individual fillings (Examples 2 and 1).
  • Example 10 shows that in the temperature range investigated a Ca zeolite X arrangement with CaO / Al203 ratios of over 80% does not bring any significant improvements, i. H. the yield cannot be improved by a highly exchanged Ca zeolite X at the outlet.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Gas Separation By Absorption (AREA)
EP96107132A 1995-05-19 1996-05-07 Procédé pour l'enrichissement en oxygène de l'air par adsorption d'air avec des mélanges de zéolithes à tamis moléculaires Expired - Lifetime EP0743281B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19518407 1995-05-19
DE19518407A DE19518407A1 (de) 1995-05-19 1995-05-19 Verfahren zur adsorptiven Sauerstoffanreicherung von Luft mit Mischungen aus Molekularsieb-Zeolithen

Publications (2)

Publication Number Publication Date
EP0743281A1 true EP0743281A1 (fr) 1996-11-20
EP0743281B1 EP0743281B1 (fr) 1998-03-18

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EP96107132A Expired - Lifetime EP0743281B1 (fr) 1995-05-19 1996-05-07 Procédé pour l'enrichissement en oxygène de l'air par adsorption d'air avec des mélanges de zéolithes à tamis moléculaires

Country Status (9)

Country Link
US (1) US5656066A (fr)
EP (1) EP0743281B1 (fr)
JP (1) JPH08309180A (fr)
CN (1) CN1070457C (fr)
AT (1) ATE164146T1 (fr)
BR (1) BR9602334A (fr)
CA (1) CA2176787A1 (fr)
DE (2) DE19518407A1 (fr)
ES (1) ES2113760T3 (fr)

Cited By (2)

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Publication number Priority date Publication date Assignee Title
EP0875279A2 (fr) * 1997-04-17 1998-11-04 Praxair Technology, Inc. Lits d'adsorbant à couches multiples pour procédé d'adsorption à pression alternée
EP0760248B1 (fr) * 1994-03-18 2003-06-11 Uop Adsorbant zéolitique pour l'adsorption sélective d'azote dans les procédés de séparation de l'air

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DE19740848A1 (de) * 1997-09-17 1999-03-18 Sgi Prozess Technik Gmbh Druckwechselanlage zur Gewinnung von Sauerstoff aus der Luft und Verfahren zum Betrieb einer solchen
FR2771656B1 (fr) * 1997-12-01 2000-01-07 Air Liquide Procede psa mettant en oeuvre un adsorbant a proprietes de capacite et/ou de selectivite heterogenes
US6391092B1 (en) * 1999-10-12 2002-05-21 The Boc Group, Inc. Thermal swing adsorption process for the removal of dinitrogen oxide, hydrocarbons and other trace impurities from air
FR2811241B1 (fr) * 2000-07-07 2002-12-13 Ceca Sa Procede pour la purification de melanges gazeux a base d'hydrogene utilisant une zeolite x au calcium
US6544318B2 (en) * 2001-02-13 2003-04-08 Air Products And Chemicals, Inc. High purity oxygen production by pressure swing adsorption
DE10300141A1 (de) 2003-01-07 2004-07-15 Blue Membranes Gmbh Verfahren und Vorrichtung zur Sauerstoffanreicherung von Luft bei gleichzeitiger Abreicherung von Kohlendioxid
DE202004021139U1 (de) 2004-01-28 2007-02-01 Apio, Inc., Guadalupe Verpackung
US7954490B2 (en) 2005-02-09 2011-06-07 Vbox, Incorporated Method of providing ambulatory oxygen
US7431032B2 (en) * 2005-02-09 2008-10-07 Vbox Incorporated Low power ambulatory oxygen concentrator
US7604005B2 (en) 2005-02-09 2009-10-20 Vbox Incorporated Adsorbent cartridge for oxygen concentrator
US7171963B2 (en) * 2005-02-09 2007-02-06 Vbox, Incorporated Product pump for an oxygen concentrator
US20060174875A1 (en) * 2005-02-09 2006-08-10 Vbox, Incorporated Ambulatory oxygen concentrator containing a power pack
US8020553B2 (en) * 2005-02-09 2011-09-20 Vbox, Incorporated Ambulatory oxygen concentrator containing a three phase vacuum separation system
US7766010B2 (en) 2005-02-09 2010-08-03 Vbox, Incorporated Method of controlling the rate of oxygen produced by an oxygen concentrator
US7866315B2 (en) 2005-02-09 2011-01-11 Vbox, Incorporated Method and apparatus for controlling the purity of oxygen produced by an oxygen concentrator
US7121276B2 (en) * 2005-02-09 2006-10-17 Vbox, Incorporated Personal oxygen concentrator
US7288189B2 (en) * 2005-02-11 2007-10-30 Bonifer Jeffery P Multi-faceted intake filter for an aquarium
JP4937259B2 (ja) 2005-07-28 2012-05-23 アピオ インク． 雰囲気制御部材の組み合わせ
US8695600B2 (en) * 2009-07-22 2014-04-15 Vbox, Incorporated Method of separating and distributing oxygen
US9149757B2 (en) 2012-11-14 2015-10-06 Oddomotive, Inc. Calcium LSX and lithium H-LSX zeolite oxygen enrichment system for an internal combustion engine

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US5656066A (en) 1997-08-12
BR9602334A (pt) 1998-04-22
DE19518407A1 (de) 1996-11-21
CN1148566A (zh) 1997-04-30
DE59600118D1 (de) 1998-04-23
ES2113760T3 (es) 1998-05-01
CN1070457C (zh) 2001-09-05
ATE164146T1 (de) 1998-04-15
CA2176787A1 (fr) 1996-11-20
JPH08309180A (ja) 1996-11-26
EP0743281B1 (fr) 1998-03-18

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